2-pyridinylcycloalkylcarboxamide derivatives as fungicides

ABSTRACT

A compound of general formula (I): 
     
       
         
         
             
             
         
       
     
     A process for preparing this compound. 
     A compound of general formula (II): 
     
       
         
         
             
             
         
       
     
     A fungicide composition comprising a compound of general formula (I). 
     A method for treating plants by applying a compound of general formula (I) or a composition comprising it.

CROSS-REFERENCE TO RELATED APPLICATION(S)

The present application is a 371 national phase conversion ofInternational Application No. PCT/2006/062389 filed 17 May 2006, whichclaims priority of European Application No. 05356083.5 filed 18 May2005.

The present invention relates to novelN-[2-(2-pyridinyl)ethyl]carboxamide derivatives, their process ofpreparation, their use as fungicides, particularly in the form offungicidal compositions, and methods for the control of phytopathogenicfungi of plants using these compounds or their compositions.

International patent application WO 01/11965 discloses a broad family offungicidal compounds. There is no specific disclosure ofN-[2-(2-pyridinyl)ethyl]carboxamide derivatives.

It is always of high-interest in the field of agrochemicals to usepesticidal compounds more active than the compounds already known by theman ordinary skilled in the art whereby less compound can be used whilstretaining equivalent efficacy.

We have now found a new family of compounds which show enhancedfungicidal activity over the general known family of such compounds.

Accordingly, the present invention relates to aN-[2-(2-pyridinyl)ethyl]carboxamide derivative of general formula (I)

-   -   in which:    -   n is 1, 2, or 3;    -   X is the same or different and is a hydrogen atom, a halogen        atom, a nitro group, a cyano group, a hydroxy group, an amino        group, a sulfanyl group, a pentafluoro-λ⁶-sulfanyl group, a        formyl group, a formyloxy group, a formylamino group, a carboxy        group, a carbamoyl group, a N-hydroxycarbamoyl group, a        carbamate group, a (hydroxyimino)-C₁-C₆-alkyl group, a        C₁-C₈-alkyl, a C₂-C₈-alkenyl, a C₂-C₈-alkynyl, a        C₁-C₈-alkylamino, a di-C₁-C₈-alkylamino, a C₁-C₈-alkoxy, a        C₁-C₈-halogenoalkoxy having 1 to 5 halogen atoms, a        C₁-C₈-alkylsulfanyl, a C₁-C₈-halogenoalkylsulfanyl having 1 to 5        halogen atoms, a C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy        having 1 to 5 halogen atoms, a C₃-C₈-alkynyloxy, a        C₃-C₈-halogenoalkynyloxy having 1 to 5 halogen atoms, a        C₃-C₈-cycloalkyl, a C₃-C₈-halogenocycloalkyl having 1 to 5        halogen atoms, a C₁-C₈-alkylcarbonyl, a        C₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms, a        C₁-C₈-alkylcarbamoyl, a di-C₁-C₈-alkylcarbamoyl, a        N—C₁-C₈-alkyl)oxycarbamoyl, a C₁-C₈-alkoxycarbamoyl, a        (N—C₁-C₈-alkyl)-C₁-C₈-alkoxycarbamoyl, a C₁-C₈-alkoxycarbonyl, a        C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a        C₁-C₈-alkylcarbonyloxy, a C₁-C₈-halogenoalkylcarbonyloxy having        1 to 5 halogen atoms, a C₁-C₈-alkylcarbonylamino, a        C₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, a        C₁-C₈-alkylaminocarbonyloxy, a di-C₁-C₈-alkylaminocarbonyloxy, a        C₁-C₈-alkyloxycarbonyloxy, a C₁-C₈-alkylsulphenyl, a        C₁-C₈-halogenoalkylsulphenyl having 1 to 5 halogen atoms, a        C₁-C₈-alkylsulphinyl, a C₁-C₈-halogenoalkylsulphinyl having 1 to        5 halogen atoms, a C₁-C₈-alkylsulphonyl, a        C₁-C₈-halogenoalkylsulphonyl having 1 to 5 halogen atoms, a        (C₁-C₆-alkoxyimino)-C₁-C₆-alkyl, a        (C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl, a        (C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl, a        (benzyloxyimino)-C₁-C₆-alkyl, a benzyloxy, a benzylsulfanyl, a        benzylamino, a phenoxy, a phenylsulfanyl or a phenylamino;    -   R^(a) is a hydrogen atom, a halogen atom, a nitro group, a cyano        group, a hydroxy group, a sulfanyl group, a        pentafluoro-λ⁶-sulfanyl group, a formyl group, a formyloxy        group, a formylamino group, a carboxy group, a carbamoyl group,        a N-hydroxycarbamoyl group, a carbamate group, a        (hydroxyimino)-C₁-C₆-alkyl group, a C₁-C₈-alkyl, a        C₂-C₈-alkenyl, a C₂-C₈-alkynyl, a C₁-C₈-alkylamino, a        di-C₁-C₈-alkylamino, a C₁-C₈-alkoxy, a C₁-C₈-halogenoalkoxy        having 1 to 5 halogen atoms, a C₁-C₈-alkylsulfanyl, a        C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms, a        C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1 to 5        halogen atoms, a C₃-C₈-alkynyloxy, a C₃-C₈-halogenoalkynyloxy        having 1 to 5 halogen atoms, a C₃-C₈-cycloalkyl, a        C₃-C₈-halogenocycloalkyl having 1 to 5 halogen atoms, a        C₁-C₈-alkylcarbonyl, a C₁-C₈-halogenoalkylcarbonyl having 1 to 5        halogen atoms, a C₁-C₈-alkylcarbamoyl, a        di-C₁-C₈-alkylcarbamoyl, a N—C₁-C₈-alkyloxycarbamoyl, a        C₁-C₈-alkoxycarbamoyl, a N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl, a        C₁-C₈-alkoxycarbonyl, a C₁-C₈-halogenoalkoxycarbonyl having 1 to        5 halogen atoms, a C₁-C₈-alkylcarbonyloxy, a        C₁-C₈-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, a        C₁-C₈-alkylcarbonylamino, a C₁-C₈-halogenoalkylcarbonylamino        having 1 to 5 halogen atoms, a C₁-C₈-alkylaminocarbonyloxy, a        di-C₁-C₈-alkylaminocarbonyloxy, a C₁-C₈-alkyloxycarbonyloxy, a        C₁-C₈-alkylsulphenyl, a C₁-C₈-halogenoalkylsulphenyl having 1 to        5 halogen atoms, a C₁-C₈-alkylsulphinyl, a        C₁-C₈-halogenoalkylsulphinyl having 1 to 5 halogen atoms, a        C₁-C₈-alkylsulphonyl, a C₁-C₈-halogenoalkylsulphonyl having 1 to        5 halogen atoms, a (C₁-C₆-alkoxyimino)-C₁-C₆-alkyl, a        (C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl, a        (C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl, a        (benzyloxyimino)-C₁-C₆-alkyl, a benzyloxy, a benzylsulfanyl, a        benzylamino, a phenoxy, a phenylsulfanyl or a phenylamino;    -   A is a 3-, 4-, 5-, 6- or 7-membered non aromatic carbocycle;    -   R¹ and R² are chosen, independently of each other, as being a        hydrogen atom, a halogen atom, a cyano group, a hydroxy group,        an amino group, a sulfanyl group, a formyl group, a formyloxy        group, a formylamino group, a carboxy group, a carbamoyl group,        a N-hydroxycarbamoyl group, a carbamate group, a        (hydroxyimino)-C₁-C₆-alkyl group, a C₁-C₆-alkyl, a        C₂-C₆-alkenyl, a C₂-C₆-alkynyl, a C₁-C₆-alkylamino, a        di-C₁-C₆-alkylamino, a C₁-C₆-alkoxy, a C₁-C₆-halogenoalkyl        having 1 to 5 halogen atoms, a C₁-C₆-halogenoalkoxy having 1 to        5 halogen atoms, a C₁-C₆-alkylsulfanyl, a        C₁-C₆-halogenoalkylsulfanyl having 1 to 5 halogen atoms, a        C₂-C₆-alkenyloxy, a C₂-C₆-halogenoalkenyloxy having 1 to 5        halogen atoms, a C₃-C₆-alkynyloxy, a C₃-C₆-halogenoalkynyloxy        having 1 to 5 halogen atoms, a C₃-C₆-cycloalkyl, a        C₃-C₆-halogenocycloalkyl having 1 to 5 halogen atoms, a        C₁-C₆-alkylcarbonyl, a C₁-C₆-halogenoalkylcarbonyl having 1 to 5        halogen atoms, a C₁-C₆-alkylcarbamoyl, a        di-C₁-C₆-alkylcarbamoyl, a N—C₁-C₆-alkyloxycarbamoyl, a        C₁-C₆-alkoxycarbamoyl, a N—C₁-C₆-alkyl-C₁-C₆-alkoxycarbamoyl, a        C₁-C₆-alkoxycarbonyl, a C₁-C₆-halogenoalkoxycarbonyl having 1 to        5 halogen atoms, a C₁-C₆-alkylcarbonyloxy, a        C₁-C₆-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, a        C₁-C₆-alkylcarbonylamino, a C₁-C₆-halogenoalkylcarbonylamino        having 1 to 5 halogen atoms, a C₁-C₆-alkylaminocarbonyloxy, a        di-C₁-C₆-alkylaminocarbonyloxy, a C₁-C₆-alkyloxycarbonyloxy, a        C₁-C₆-alkylsulphenyl, a C₁-C₆-halogenoalkylsulphenyl having 1 to        5 halogen atoms, a C₁-C₆-alkylsulphinyl, a        C₁-C₆-halogenoalkylsulphinyl having 1 to 5 halogen atoms, a        C₁-C₆-alkylsulphonyl, a C₁-C₆-halogenoalkylsulphonyl having 1 to        5 halogen atoms, a benzyl, a benzyloxy, a benzylsulfanyl, a        benzylsulfinyl, a benzylsulfonyl, a benzylamino, a phenoxy, a        phenylsulfanyl, a phenylsulfinyl, a phenylsulfonyl, a        phenylamino, a phenylcarbonylamino, a 2,6        dichlorophenyl-carbonylamino group or a phenyl group,    -   R³ is chosen as being a hydrogen atom, a cyano group, a formyl        group, a hydroxy group, a C₁-C₆-alkyl, a C₁-C₆-halogenoalkyl        having 1 to 5 halogen atoms, a C₁-C₆-alkoxy, a        C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, a        C₂-C₆-alkenyl, a C₂-C₆-alkynyl, a C₁-C₆-alkoxy-C₁-C₆-alkyl, a        C₁-C₆-cyanoalkyl, a C₁-C₆-aminoalkyl, a        C₁-C₆-alkylamino-C₁-C₆-alkyl, a di-C₁-C₆-alkylamino-C₁-C₆-alkyl,        a C₁-C₆-alkylcarbonyl, a C₁-C₆-halogenalkylcarbonyl having 1 to        5 halogen atoms, a C₁-C₆-alkyloxycarbonyl, a C₃-C₇-cycloalkyl, a        C₃-C₇-halogenocycloalkyl having 1 to 5 halogen atoms, a        C₃-C₇-cycloalkyl-C₁-C₆-alkyl, a C₁-C₆-benzyloxycarbonyl, a        C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl, a C₁-C₆-alkylsulfonyl or a        C₁-C₆-halogenoalkylsulfonyl having 1 to 5 halogen atoms; and    -   Het represents an optionally substituted 5-, 6- or 7-membered        non-fused heterocycle with one, two or three heteroatoms which        may be the same or different, Het being linked by a carbon atom;

as well as its salts, N-oxydes, metallic complexes, metalloidiccomplexes and optically active isomers.

In the context of the present invention:

halogen means fluorine, bromine, chlorine or iodine.

carboxy means —C(═O)OH; carbonyl means —C(═O)—; carbamoyl means—C(═O)NH₂; N-hydroxycarbamoyl means —C(═O)NHOH;

an alkyl group, an alkenyl group, and an alkynyl group as well asmoieties containing these terms, can be linear or branched.

In the context of the present invention, it has also to be understoodthat in the case of di-substituted amino and of di-substituted carbamoylradicals, the two substituents may form together with the nitrogen atombearing them a saturated heterocyclic ring containing 3 to 7 atoms.

Any of the compound of the present invention can exist in one or moreoptical or chiral isomer forms depending on the number of asymmetriccentres in the compound. The invention thus relates equally to all theoptical isomers and to their racemic or scalemic mixtures (the term“scalemic” denotes a mixture of enantiomers in different proportions),and to the mixtures of all the possible stereoisomers, in allproportions. The diastereoisomers and/or the optical isomers can beseparated according to the methods which are known per se by the manordinary skilled in the art.

Any of the compound of the present invention can also exist in one ormore geometric isomer forms depending on the number of double bonds inthe compound. The invention thus relates equally to all geometricisomers and to all possible mixtures, in all proportions. The geometricisomers can be separated according to general methods, which are knownper se by the man ordinary skilled in the art.

Any of the compound of general formula (I) wherein R₁ represents ahydroxy or sulfanyl group, and/or X represents a hydroxy, sulfanyl oramino group, may be found in its tautomeric form resulting of the shiftof the proton of said hydroxy, sulfanyl or amino group. Such tautomericforms of such compounds are also part of the present invention. Moregenerally speaking, all tautomeric forms of compounds of general formula(I) wherein R₁ represents a hydroxy or sulfanyl group, and/or Xrepresents a hydroxy, sulfanyl or amino group, as well as the tautomericforms of the compounds which can optionally be used as intermediates inthe preparation processes, and which will be defined in the descriptionof these processes, are also part of the present invention.

According to the present invention, the 2-pyridyl is substituted in6-position by R^(a) and may be substituted in any other position by(X)_(n), in which R^(a), X and n are as defined above. Preferably, thepresent invention relates to N-[2-(2-pyridinyl)ethyl]carboxamidederivative of general formula (I) in which the different characteristicsmay be chosen alone or in combination as being:

as regards R^(a), R^(a) is a hydrogen atom or a halogen atom;

as regards n, n is 1 or 2;

as regards X, X is a halogen atom or a C₁-C₈-alkyl;

as regards the positions in which the 2-pyridyl moiety is substituted byX, the 2-pyridyl moiety is substituted by X in 3- and/or in 5-position.

According to the present invention, A is a 3-, 4-, 5-, 6- or 7-memberednon aromatic carbocycle. Preferably, A is a 3-, 5-, 6- or 7-membered nonaromatic carbocycle. Even more preferably, A is chosen from cyclopropyl,cyclopentyl, cyclohexyl and cycloheptyl.

According to the present invention, two of the carbon atoms of thecycloalkyl moiety of the compound of formula (I) are respectivelysubstituted by R¹ and R². Preferably, the present invention also relatesto N-[2-(2-pyridinyl)cycloalkyl]carboxamide derivative of generalformula (I) in which R¹ and R² may be chosen, independently of eachother, as being a hydrogen atom, a halogen atom, a cyano group, ahydroxy group, a C₁-C₆-alkyl, a C₁-C₆-halogenoalkyl having 1 to 5halogen atoms, a C₂-C₆-alkenyl, a C₁-C₆-alkoxy, a C₁-C₆-alkylsulfanyl, aC₁-C₆-alkylsulfenyl, a C₁-C₆-alkylsulfinyl, a C₁-C₆-alkoxycarbonyl, aC₁-C₆-alkylcarbonylamino, a C₁-C₆-alkoxycarbonyloxy, aC₁-C₆-alkoxycarbonylamino or a phenyl group. More preferably, R¹ and R²may be chosen, independently of each other, as being a hydrogen atom, ahalogen atom, a C₁-C₆-alkyl, a C₁-C₆-halogenoalkyl having 1 to 5 halogenatoms or a C₁-C₆-alkylcarbonylamino. Even more preferably, R¹ and R² areboth a hydrogen atom.

According to the present invention, the nitrogen atom of the carboxamidemoiety of the compound of formula (I) is substituted by R³, R³ being asdefined above. Preferably, the present invention also relates toN-[2-(2-pyridinyl)cycloalkyl]carboxamide derivative of general formula(I) in which R³ may be chosen as being a hydrogen atom or aC₃-C₇-cycloalkyl. Even more preferably, the C₃-C₇-cycloalkyl iscyclopropyl.

According to the present invention, “Het” of the compound of generalformula (I) is a 5-, 6- or 7-membered non-fused heterocycle with one,two or three heteroatoms which may be the same or different, Het beinglinked by a carbon atom and being optionally substituted. Preferably,Het is substituted in ortho position.

According to the present invention, “Het” of the compound of generalformula (I) may be a five membered ring heterocycle. Specific examplesof compounds of the present invention where Het is a five memberedheterocycle include:

Het may represent a heterocycle of the general formula (Het-1)

-   -   in which:    -   R⁴ and R⁵ may be the same or different and may be a hydrogen        atom, a halogen atom, an amino group, a nitro group, a        C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5 halogen        atoms; and    -   R⁶ may be a halogen atom, a nitro group, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-2)

-   -   in which:    -   R⁷ may be a hydrogen atom, a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and    -   R⁸ and R⁹ may be the same or different and may be a hydrogen        atom, a halogen atom, an amino group, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms;

provided that the R⁷ and R⁹ are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-3)

-   -   in which:    -   R¹⁰ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and    -   R¹¹ may be a hydrogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-4)

-   -   in which:    -   R¹² and R¹³ may be the same or different and may be a hydrogen        atom, a halogen atom, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl        having 1 to 5 halogen atoms, a C₁-C₄-alkylthio, a        C₁-C₄-alkylsulphonyl, a phenyl optionally substituted by a        halogen atom or a C₁-C₄-alkyl or a pyridyl optionally        substituted by a halogen atom or a C₁-C₄-alkyl; and    -   R¹⁴ may be a halogen atom, a cyano group, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms or a        C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-5)

-   -   in which:    -   R¹⁵ and R¹⁶ may be the same or different and may be a hydrogen        atom, a halogen atom, a C₁-C₄-alkyl, a C₁-C₄-alkyloxy or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and    -   R¹⁷ may be a hydrogen atom, a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms;

provided that the R¹⁶ and R¹⁷ are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-6)

-   -   in which:    -   R¹⁸ may be a hydrogen atom, a halogen atom, a cyano group, a        C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5 halogen        atoms;    -   R¹⁹ and R²¹ may be the same or different and may be a hydrogen        atom, a halogen atom, a C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl        having 1 to 5 halogen atoms; and    -   R²⁰ may be a hydrogen atom, a cyano group, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a        C₁-C₄-alkoxy-C₁-C₄-alkyl, a hydroxy-C₁-C₄-alkyl, a        C₁-C₄-alkylsulphonyl, a di(C₁-C₄-alkyl)aminosulphonyl, a        C₁-C₆-alkylcarbonyl, a phenylsulphonyl optionally substituted by        a halogen atom or a C₁-C₄-alkyl, or a benzoyl optionally        substituted by a halogen atom or a C₁-C₄-alkyl;

provided that the R¹⁸ and R²¹ are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-7)

-   -   in which:    -   R²² may be a hydrogen atom, a cyano group, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a        C₁-C₄-alkoxy-C₁-C₄-alkyl, a hydroxy-C₁-C₄-alkyl, a        C₁-C₄-alkylsulphonyl, a di(C₁-C₄-alkyl)aminosulphonyl, a        C₁-C₆-alkylcarbonyl, a phenylsulphonyl optionally substituted by        a halogen atom or a C₁-C₄-alkyl, or a benzoyl optionally        substituted by a halogen atom or a C₁-C₄-alkyl; and    -   R²³, R²⁴ and R²⁵ may be the same or different and may be a        hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms or a        C₁-C₄-alkylcarbonyl;

provided that R²² and R²⁵ are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-8)

-   -   in which:    -   R²⁶ may be a hydrogen atom or a C₁-C₄-alkyl; and    -   R²⁷ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-9)

-   -   in which:    -   R²⁸ may be a hydrogen atom or a C₁-C₄-alkyl; and    -   R²⁹ may be a halogen atom, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl        having 1 to 5 halogen atoms or a phenyl optionally substituted        by a halogen atom or a C₁-C₄-alkyl.

Het may represent a heterocycle of the general formula (Het-10)

-   -   in which:    -   R³⁰ may be a hydrogen atom, a halogen atom, an amino group, a        cyano group, a C₁-C₄-alkylamino, a di-(C₁-C₄-alkyl)amino, a        C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms        or a phenyl optionally substituted by a halogen atom or a        C₁-C₄-alkyl; and    -   R³¹ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-11)

-   -   in which:    -   R³² may be a hydrogen atom, a halogen atom, an amino group, a        cyano group, a C₁-C₄-alkylamino, a di-(C₁-C₄-alkyl)amino, a        C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5 halogen        atoms; and    -   R³³ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-12)

-   -   in which:    -   R³⁴ may be a halogen atom, a cyano group, a nitro group, a        C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms,        a C₃-C₆-cycloalkyl, a C₁-C₄-alkoxy, a C₁-C₄-halogenoalkoxy        having 1 to 5 halogen atoms, a C₁-C₄-alkylthio, a        C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, an        aminocarbonyl group or an aminocarbonyl-C₁-C₄-alkyl;    -   R³⁵ may be a hydrogen atom, a halogen atom, a cyano group, a        nitro group, a C₁-C₄-alkyl, a C₁-C₄-alkoxy or a C₁-C₄-alkylthio;        and    -   R³⁶ may be a hydrogen atom, a phenyl, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a        hydroxy-C₁-C₄-alkyl, a C₂-C₆-alkenyl, a C₃-C₆-cycloalkyl, a        C₁-C₄-alkylthio-C₁-C₄-alkyl, a        C₁-C₄-halogenoalkylthio-C₁-C₄-alkyl having 1 to 5 halogen atoms,        a C₁-C₄-alkoxy-C₁-C₄-alkyl or a C₁-C₄-halogenoalkoxy-C₁-C₄-alkyl        having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-13)

-   -   in which:    -   R³⁷ may be a hydrogen atom, a halogen atom, a cyano group, a        nitro group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5        halogen atoms, a C₃-C₆-cycloalkyl, a C₁-C₄-alkoxy, a        C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a        C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen        atoms, an aminocarbonyl or an aminocarbonyl-C₁-C₄-alkyl;    -   R³⁸ may be a hydrogen atom, a halogen atom, a cyano group, a        C₁-C₄-alkyl, a C₁-C₄-alkoxy, a C₁-C₄-halogenoalkoxy having 1 to        5 halogen atoms or a C₁-C₄-alkylthio; and    -   R³⁹ may be a hydrogen atom, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl        having 1 to 5 halogen atoms, a hydroxy-C₁-C₄-alkyl, a        C₂-C₆-alkenyl, a C₃-C₆-cycloalkyl, a        C₁-C₄-alkylthio-C₁-C₄-alkyl, a        C₁-C₄-halogenoalkylthio-C₁-C₄-alkyl having 1 to 5 halogen atoms,        a C₁-C₄-alkoxy-C₁-C₄-alkyl, a C₁-C₄-halogenoalkoxy-C₁-C₄-alkyl        having 1 to 5 halogen atoms or a phenyl optionally substituted        by a halogen atom, a C₁-C₄-alkyl, a C₁-C₄-alkoxyalkyl or a nitro        group;

provided that the R³⁷ and R³⁸ are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-14)

-   -   in which:    -   R⁴⁰ may be a hydrogen atom, a halogen atom, a cyano group, a        nitro group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5        halogen atoms, a C₃-C₆-cycloalkyl, a C₁-C₄-alkoxy, a        C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a        C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen        atoms, an aminocarbonyl, or an aminocarbonyl-C₁-C₄-alkyl;    -   R⁴¹ may be a hydrogen atom, a halogen atom, a cyano group, a        C₁-C₄-alkyl, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms;    -   R⁴² may be a hydrogen atom, a phenyl, a benzyl, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a        hydroxy-C₁-C₄-alkyl, a C₂-C₆-alkenyl, a C₃-C₆-cycloalkyl, a        C₁-C₄-alkylthio-C₁-C₄-alkyl, a        C₁-C₄-halogenoalkylthio-C₁-C₄-alkyl having 1 to 5 halogen atoms,        a C₁-C₄-alkoxy-C₁-C₄-alkyl, a C₁-C₄-halogenoalkoxy-C₁-C₄-alkyl        having 1 to 5 halogen atoms;

provided that R⁴¹ and R⁴² are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-15)

-   -   in which:    -   R⁴³ may be a hydrogen atom, a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and    -   R⁴⁴ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-16)

-   -   in which R⁴⁵ and R⁴⁶ may be the same or different and may be a        hydrogen atom, a halogen atom, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a phenyl        optionally substituted by a halogen atom or a C₁-C₄-alkyl, or a        heterocyclyl optionally substituted by a halogen atom or a        C₁-C₄-alkyl;

provided that R⁴⁷ and R⁴⁸ are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-17)

-   -   in which    -   R⁴⁷ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms. and    -   R⁴⁸ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-18)

-   -   in which R⁴⁹ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

Het may represent a heterocycle of the general formula (Het-19)

-   -   in which:    -   R⁵⁰ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and    -   R⁵¹ may be a hydrogen atom, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl        having 1 to 5 halogen atoms, or a phenyl optionally substituted        by a halogen atom or a C₁-C₄-alkyl.

Het may represent a heterocycle of the general formula (Het-20)

-   -   in which R⁵² may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

According to the present invention, “Het” of the compound of generalformula (I) may be a six membered ring heterocycle. Specific examples ofcompounds of the present invention where Het is a six memberedheterocycle include:

Het may represent a heterocycle of the general formula (Het-21)

-   -   in which:    -   R⁵³ may be a halogen atom, a hydroxy group, a cyano group, a        C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms,        a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio        having 1 to 5 halogen atoms or a C₁-C₄-halogenoalkoxy having 1        to 5 halogen atoms;    -   R⁵⁴, R⁵⁵ and R⁵⁶, which may be the same or different, may be a        hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy,        a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen        atoms, a C₁-C₄-alkylsulphinyl or a C₁-C₄-alkylsulphonyl.

Het may represent a heterocycle of the general formula (Het-22)

-   -   in which:    -   R⁵⁷ may be a hydrogen atom, a halogen atom, a hydroxy group, a        cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5        halogen atoms, a C₁-C₄-alkoxy, a C₁-C₅-alkylthio, a        C₂-C₅-alkenylthio a C₁-C₄-halogenoalkylthio having 1 to 5        halogen atoms, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen        atoms, a phenyloxy optionally substituted by a halogen atom or a        C₁-C₄-alkyl, or a phenylthio optionally substituted by a halogen        atom or a C₁-C₄-alkyl;    -   R⁵⁸, R⁵⁹ and R⁶⁰, which may the same or different, may be a        hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy,        a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen        atoms, a C₁-C₄-alkylsulphinyl, a C₁-C₄-alkylsulphonyl or a        N-morpholine optionally substituted by a halogen atom or a        C₁-C₄-alkyl, or a thienyl optionally substituted by a halogen        atom or a C₁-C₄-alkyl;

provided that the R⁵⁷ and R⁶⁰ are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-23)

-   -   in which R⁶¹, R⁶², R⁶³ and R⁶⁴, which may be the same or        different, may be a hydrogen atom, a halogen atom, a hydroxy        group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl        having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio,        a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a        C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a        C₁-C₄-alkylsulphinyl or a C₁-C₄-alkylsulphonyl;

provided that the R⁶¹ and R⁶⁴ are not both a hydrogen atom.

Het may represent a heterocycle of the general formula (Het-24)

-   -   in which:    -   R⁶⁵ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms;    -   R⁶⁶ may be a hydrogen atom, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl        having 1 to 5 halogen atoms, a C₁-C₆-alkoxycarbonyl, a benzyl        optionally substituted by 1 to 3 halogen atoms, a        benzyloxycarbonyl optionally substituted by 1 to 3 halogen atoms        or a heterocyclyl.

Het may represent a heterocycle of the general formula (Het-25)

-   -   in which:    -   R⁶⁷ may be a halogen atom, a hydroxy group, a cyano group, a        C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms,        a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio        having 1 to 5 halogen atoms or a C₁-C₄-halogenoalkoxy having 1        to 5 halogen atoms;    -   R⁶⁸ may be a hydrogen atom, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl        having 1 to 5 halogen atoms or a benzyl.

Het may represent a heterocycle of the general formula (Het-26)

-   -   in which:    -   X¹ may be a sulphur atom, —SO—, —SO₂— or —CH₂—;    -   R⁶⁹ may be a C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5        halogen atoms; and    -   R⁷⁰ and R⁷¹ may be the same or different and may be a hydrogen        atom or a C₁-C₄-alkyl.

Het may represent a heterocycle of the general formula (Het-27)

-   -   in which:    -   R⁷² may be a C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5        halogen atoms;

Het may represent a heterocycle of the general formula (Het-28)

-   -   in which:    -   R⁷³ may be a C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5        halogen atoms.

Het may represent a heterocycle of the general formula (Het-29)

-   -   in which R⁷⁴ may be a halogen atom, a C₁-C₄-alkyl or a        C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

The present invention also relates to a process for the preparation ofthe compound of general formula (I). Thus, according to a further aspectof the present invention there is provided a process for the preparationof compound of general formula (I) as defined above, which comprisesreacting a 2-pyridine derivative of general formula (II) or one of itssalt:

in which X, n, R^(a), R¹, R² and A are as defined above; with acarboxylic acid derivative of the general formula (III)

in which:

L¹ is a leaving group chosen as being a halogen atom, a hydroxyl group,—OR⁷⁵, —OCOR⁷⁵, R⁷⁵ being a C₁-C₆ alkyl, a C₁-C₆ haloalkyl, a benzyl,4-methoxybenzyl, pentafluorophenyl or a group of formula

in the presence of a catalyst and, if L¹ is a hydroxyl group, in thepresence of a condensing agent.

The process according to the present invention is conducted in thepresence of a catalyst. Suitable catalyst may be chosen as being4-dimethyl-aminopyridine, 1-hydroxy-benzotriazole or dimethylformamide.

In case L¹ is a hydroxy group, the process according to the presentinvention is conducted in the presence of condensing agent. Suitablecondensing agent may be chosen as being acid halide former, such asphosgene, phosphorous tribromide, phosphorous trichloride, phosphorouspentachloride, phosphorous trichloride oxide or thionyl chloride;anhydride former, such as ethyl chloroformate, methyl chloroformate,isopropyl chloroformate, isobutyl chloroformate ormethanesulfonyl-chloride; carbodiimides, such asN,N′-dicyclohexylcarbodiimide (DCC) or other customary condensingagents, such as phosphorous pentoxide, polyphosphoric acid,N,N′-carbonyl-diimidazole,2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ),triphenylphosphine/tetrachloromethane,4-(4,6-dimethoxy[1.3.5]triazin-2-yl)-4-methylmorpholinium chloridehydrate or bromo-tripyrrolidino-phosphonium-hexafluorophosphate.

When R³ is a hydrogen atom, the above mentioned process for thepreparation of compound of general formula (I) may optionally becompleted by a further step according to the following reaction scheme:

in which:

-   -   R¹, R², A, R^(a), X, n and Het are as defined above;    -   R^(3a) is chosen as being a cyano group, a formyl group, a        hydroxy group, a C₁-C₆-alkyl, a C₁-C₆-halogenoalkyl having 1 to        5 halogen atoms, a C₁-C₆-alkoxy, a C₁-C₆-halogenoalkoxy having 1        to 5 halogen atoms, a C₃-C₆-halogenocycloalkyl having 1 to 5        halogen atoms, a C₂-C₆-alkenyl, a C₂-C₆-alkynyl, a        C₁-C₆-alkoxy-C₁-C₆-alkyl, a C₁-C₆-cyanoalkyl, a        C₁-C₆-aminoalkyl, a C₁-C₆-alkylamino-C₁-C₆-alkyl, a        di-C₁-C₆-alkylamino-C₁-C₆-alkyl, a C₁-C₆-alkylcarbonyl, a        C₁-C₆-halogenalkylcarbonyl having 1 to 5 halogen atoms, a        C₁-C₆-alkyloxycarbonyl, a C₃-C₇-cycloalkyl, a        C₃-C₇-halogenocycloalkyl having 1 to 5 halogen atoms, a        C₃-C₇-cycloalkyl-C₁-C₆-alkyl, a C₁-C₆-benzyloxycarbonyl, a        C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl, a C₁-C₆-alkylsulfonyl or a        C₁-C₆-halogenoalkylsulfonyl having 1 to 5 halogen atoms; and    -   L² is a leaving group chosen as being a halogen atom, a 4-methyl        phenylsulfonyloxy or a methylsulfonyloxy;        comprising the reaction of a compound of general formula (Ia)        with a compound of general formula (XXI) to provide a compound        of general formula (I).

Depending on the definition of A, R¹, R², R³, amine derivatives ofgeneral formula (II) may be prepared by different processes. One example(a) of such a process may be when:

-   -   R¹, R², A, R^(a), X, n are as defined above;    -   R³ is a hydrogen atom, a C₁-C₆ alkyl, a C₁-C₆ haloalkyl, a C₁-C₆        alkoxy or a C₃-C₇ cycloalkyl;        then, the amine derivative of general formula (II) may be        prepared according to a process comprising:

a first step according to reaction scheme a-1:

in which:

-   -   R^(a), A, X and n are as defined above;    -   R⁷⁶ and R⁷⁷ are a C₁-C₆ alkyl or may form a 5-, 6- or 7-membered        carbocyclic or heterocyclic ring;    -   U is a leaving group chosen as being a halogen, a C₁-C₆        alkylsulfonate or a C₁-C₆ haloalkylsulfonate;        comprising the arylation of an enamine derivative of general        formula (V) by a pyridine derivative of general formula (IV), to        provide a 2-(pyridyl)ketone derivative of general formula (VIa),        at a temperature of from 0° C. to 200° C.;

a second step according to reaction scheme a-2:

in which:

-   -   R^(a), A, X and n are as defined above;    -   R¹ is a C₁-C₆ alkyl;    -   W is a halogen atom, a C₁-C₆ alkylsulfonate, a C₁-C₆        haloalkylsulfonate or a 4-methyl-phenylsulfonate,

comprising the alkylation of a compound of general formula (VIa) by areagent of general formula (VII) to provide a compound of generalformula (VIb);

a third step according to reaction scheme a-3

in which:

-   -   R^(a), A, X and n are as defined above;    -   R¹ is a hydrogen atom or a C₁-C₆ alkyl;    -   R³ is a hydrogen atom, a C₁-C₆ alkyl, a C₁-C₆ haloalkyl, a C₁-C₆        alkoxy or a C₃-C₇ cycloalkyl;        comprising the reaction of a compound of general formula (VIa)        or (VIb) with an amine of formula R³—NH2 to provide an imine        derivative of general formula (VIII);

a fourth step according to scheme a-4:

in which:

-   -   R^(a), A, X and n are as defined above;    -   R¹ is a hydrogen atom, a C₁-C₆ alkyl,    -   R³ is a hydrogen atom, a C₁-C₆ alkyl, a C₁-C₆ haloalkyl, a C₁-C₆        alkoxy or a C₃-C₇ cycloalkyl;        comprising the reduction of an imine derivative of general        formula (VIII) by hydrogenation or by an hydride donor, in the        same or a different pot to provide an amine derivative of        general formula (IIa) or one of its salt.

A second example (b) of such a process may be when:

R^(a), R², R³, A, X and n are as defined above;

R¹ is a hydrogen atom;

then, the amine derivative of general formula (II) may be preparedaccording to a process comprising:

a first step according to reaction scheme b-1:

in which:

-   -   R^(a), R², A, X and n are as defined above;    -   U is a leaving group chosen as being a halogen, a C₁-C₆        alkylsulfonate or a C₁-C₆ haloalkylsulfonate;    -   M is a metal or a metalloid specie;        comprising a coupling reaction of a pyridine derivative of        general formula (IV) with a vinylic specie of general formula        (IX), at a temperature of from 0° C. to 200° C., to provide a        compound of general formula (X);

a second step according to reaction scheme b-2:

in which R^(a), R², A, X and n are as defined above;

comprising the addition of a phthalimide or one of its salt on acompound of general formula (X) to provide a compound of general formula(XI);

a third step according to reaction scheme b-3

in which R^(a), R², A, X and n are as defined above;

comprising the de-protection of a compound of general formula (XI) withhydrazine hydrate or an hydrazine salt, to provide an amine derivativeof general formula (IIb) or one of its salts.

The first step (step b-1) of the process b according to the presentinvention is conducted in the presence of a vinylic specie of generalformula (IX) in which M can be a metal or a metalloid specie. PreferablyM is a tin derivative or a boron derivative. More preferably M is atri-nbutyltin group.

The first step (step b-1) of the process b according to the presentinvention is conducted at a temperature of from 0° C. to 200° C.

The first step (step b-1) of the process b according to the presentinvention may be conducted in the presence of a solvent. Preferably, thesolvent is chosen as being water, an organic solvent or a mixture ofboth. Suitable organic solvents may for example be aliphatic, alicyclicor aromatic solvent.

The first step (step b-1) of the process b according to the presentinvention may also be conducted in the presence of a catalyst.Preferably, the catalyst is chosen as being palladium salts orcomplexes. More preferably, the catalyst is chosen as being a palladiumcomplex. Suitable palladium complex catalyst may for example begenerated directly in the reaction mixture by separately adding to thereaction mixture a palladium salt and a complex ligand. Suitable ligandsmay for example be bulky phosphines or arsines ligands, such as(R)-(−)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphineand its corresponding enantiomer, or a mixture of both;(R)-(−)-1[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphineand its corresponding enantiomer, or a mixture of both;(R)-(−)-1[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphineand its corresponding enantiomer, or a mixture of both; or(R)-(−)-1[(S)-2-(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphineand its corresponding enantiomer, or a mixture of both.

The first step (step b-1) of the process b according to the presentinvention may also be conducted in the presence of a base. Preferably,the base is chosen as being an inorganic or an organic base. Suitableexamples of such bases may for example be alkaline earth metal or alkalimetal hydrides, hydroxides, amides, alcoholates, carbonates or hydrogencarbonates, acetates or tertiary amines.

A third example (c) of such a process may be when:

-   -   R^(a), R¹, X, n are as defined above;    -   R², R³ are a hydrogen atom    -   A is a cyclopropyl ring;        then, the amine derivative of general formula (II) may be        prepared according to a process comprising:

a first step according to reaction scheme c-1:

in which:

-   -   R^(a), R¹, X, n are as defined above;    -   U is a leaving group chosen as being a halogen, a C₁-C₆        alkylsulfonate or a C₁-C₆ haloalkylsulfonate;    -   M is a metal or a metalloid specie;        comprising a coupling reaction of a pyridine derivative of        general formula (IV) with a vinylic specie of general formula        (XII), at a temperature of from 0° C. to 200° C., to provide a        compound of general formula (XIII);

a second step according to reaction scheme c-2:

in which:

-   -   R^(a), R¹, X and n are as defined above;    -   R⁷⁸ is a C₁-C₆ alkyl group;        comprising a cyclopropanation reaction of a vinylic pyridine        derivative of general formula (XIII) with a diazo specie of        general formula (XIV), at a temperature of from 0° C. to 200°        C., to provide a compound of general formula (XV);

a third step according to reaction scheme c-3

in which:

-   -   R^(a), R¹, X and n are as defined above;    -   R⁷⁸ is a C₁-C₆ alkyl group;        comprising an amidification reaction of a ester derivative of        general formula (XV) to provide a compound of general formula        (XVI);

a fourth step according to reaction scheme c-4:

in which R^(a), R¹, X and n are as defined above;

comprising a rearrangement reaction of a primary amide derivative ofgeneral formula (XVI) in presence of a halogenating agent, to provide anamine of general formula (IIc).

The first step (step c-1) of the process c according to the presentinvention is conducted in the presence of a vinylic specie of generalformula (XII) in which M can be a metal or a metalloid specie.Preferably M is a tin derivative or a boron derivative. More preferablyM is a tri-nbutyltin group.

The first step (step c-1) of the process c according to the presentinvention is conducted at a temperature of from 0° C. to 200° C.

The first step (step c-1) of the process c according to the presentinvention may be conducted in the presence of a solvent. Preferably, thesolvent is chosen as being water, an organic solvent or a mixture ofboth. Suitable organic solvents may for example be aliphatic, alicyclicor aromatic solvent.

The first step (step c-1) of the process c according to the presentinvention may also be conducted in the presence of a catalyst.Preferably, the catalyst is chosen as being palladium salts orcomplexes. More preferably, the catalyst is chosen as being a palladiumcomplex. Suitable palladium complex catalyst may for example begenerated directly in the reaction mixture by separately adding to thereaction mixture a palladium salt and a complex ligand. Suitable ligandsmay for example be bulky phosphines or arsines ligands, such as(R)-(−)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphineand its corresponding enantiomer, or a mixture of both;(R)-(−)-1[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphineand its corresponding enantiomer, or a mixture of both;(R)-(−)-1[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphineand its corresponding enantiomer, or a mixture of both; or(R)-(−)-1[(S)-2-(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphineand its corresponding enantiomer, or a mixture of both.

The first step (step c-1) of the process c according to the presentinvention may also be conducted in the presence of a base. Preferably,the base is chosen as being an inorganic or an organic base. Suitableexamples of such bases may for example be alkaline earth metal or alkalimetal hydrides, hydroxides, amides, alcoholates, carbonates or hydrogencarbonates, acetates or tertiary amines.

The present invention also relates to another process for thepreparation of the compound of general formula (I). Thus, according to afurther aspect of the present invention there is provided a process forthe preparation of compound of general formula (I)

-   -   in which:    -   R^(a), R¹, X, Y, n, p are as defined above;    -   R² and R³ are a hydrogen atom; and    -   A is a cyclopropyl ring;        said process comprising:

a first step according to reaction scheme d-1:

in which:

-   -   R^(a), R¹, X, n are as defined above;    -   U is a leaving group chosen as being a halogen, a C₁-C₆        alkylsulfonate or a C₁-C₆ haloalkylsulfonate;    -   M is a metal or a metalloid specie;        comprising a coupling reaction of a pyridine derivative of        general formula (IV) with a vinylic specie of general formula        (XII), at a temperature of from 0° C. to 200° C., to provide a        compound of general formula (XIII);

a second step according to reaction scheme d-2:

in which:

-   -   R^(a), R¹, X and n are as defined above;    -   R⁷⁹ is a C₁-C₆ alkyl group;        comprising a cyclopropanation reaction of a vinylic pyridine        derivative of general formula (XIII) with a diazo specie of        general formula (XIV), at a temperature of from 0° C. to 200°        C., to provide a compound of general formula (XV);

a third step according to reaction scheme d-3

in which:

-   -   R^(a), R¹, X and n are as defined above;    -   R⁷⁹ is a C₁-C₆ alkyl group;        comprising a hydrolysis reaction of an ester derivative of        general formula (XV) to provide an acid of general formula        (XVII);

a fourth step according to reaction scheme d-4:

-   -   in which:    -   R^(a), R¹, X and n are as defined above; and    -   R⁸⁰ is a C₁-C₆ alkyl, C₁-C₆ halogenoalkyl, a benzyl, an allyl, a        methoxymethyl, 2-trimethylsilyl-ethyl group;        comprising a conversion of an acid derivative of general        formula (XVII) into an isocyanate of general formula (XVIII)        which is trapped in situ by an alcohol of general formula        R⁸⁰—OH, to provide a carbamate of general formula (XIX);

a fifth step according to reaction scheme d-5:

-   -   in which:    -   R^(a), R¹, X, Y, n and p are as defined above; and    -   R⁸⁰ is a C₁-C₆ alkyl, C₁-C₆ halogenoalkyl, a benzyl, an allyl, a        methoxymethyl, 2-trimethylsilyl-ethyl group;        comprising an acylation of a carbamate derivative of general        formula (XIX) to provide a compound of general formula (XX);

a sixth step according to reaction scheme d-6:

-   -   in which:    -   R^(a), R¹, X, Y, n and p are as defined above; and    -   R⁸⁰ is a C₁-C₆ alkyl, C₁-C₆ halogenoalkyl, a benzyl, an allyl, a        methoxymethyl, 2-trimethylsilyl-ethyl group;        comprising an de-protection of a carbamate derivative of general        formula (XX) to provide a compound of general formula Ic;

The first step (step d-1) of the process c according to the presentinvention is conducted in the presence of a vinylic specie of generalformula (XII) in which M can be a metal or a metalloid specie.Preferably M is a tin derivative or a boron derivative. More preferablyM is a tri-nbutyltin group.

The first step (step d-1) of the process d according to the presentinvention is conducted at a temperature of from 0° C. to 200° C.

The first step (step d-1) of the process d according to the presentinvention may be conducted in the presence of a solvent. Preferably, thesolvent is chosen as being water, an organic solvent or a mixture ofboth. Suitable organic solvents may for example be aliphatic, alicyclicor aromatic solvent.

The first step (step d-1) of the process d according to the presentinvention may also be conducted in the presence of a catalyst.Preferably, the catalyst is chosen as being palladium salts orcomplexes. More preferably, the catalyst is chosen as being a palladiumcomplex. Suitable palladium complex catalyst may for example begenerated directly in the reaction mixture by separately adding to thereaction mixture a palladium salt and a complex ligand. Suitable ligandsmay for example be bulky phosphines or arsines ligands, such as(R)-(−)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphineand its corresponding enantiomer, or a mixture of both;(R)-(−)-1[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphineand its corresponding enantiomer, or a mixture of both;(R)-(−)-1[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphineand its corresponding enantiomer, or a mixture of both; or(R)-(−)-1[(S)-2-(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphineand its corresponding enantiomer, or a mixture of both.

The first step (step d-1) of the process d according to the presentinvention may also be conducted in the presence of a base. Preferably,the base is chosen as being an inorganic or an organic base. Suitableexamples of such bases may for example be alkaline earth metal or alkalimetal hydrides, hydroxides, amides, alcoholates, carbonates or hydrogencarbonates, acetates or tertiary amines.

The fourth step (step d-4) of the process d according to the presentinvention is conducted at a temperature of from −10° C. to 200° C.

The fourth step (step d-4) of the process d according to the presentinvention is conducted in the presence of a base. Preferably, the baseis chosen as being an organic base. Suitable examples of such bases mayfor example be tertiary amines.

The fourth step (step d-4) of the process d according to the presentinvention is conducted in the presence of an azide donor. Preferably,the azide donor is chosen as being a phosphoryl azide. Suitable examplesof such phosphoryl azides may for example be diphenylphosphoryl azide.

The fourth step (step d-4) of the process d according to the presentinvention is conducted in the presence of an alcohol. Preferably, thealcohol is chosen as being a C₁-C₆ alcohol. Suitable examples of suchC₁-C₆ alcohol may for example be Tert-butanol.

The fifth step (step d-5) of the process d according to the presentinvention is conducted at a temperature of from −80° C. to 200° C.

The fifth step (step d-5) of the process d according to the presentinvention is conducted in the presence of a base. Preferably, the baseis chosen as being an inorganic or an organic base. Suitable examples ofsuch bases may for example be alkaline earth metal or alkali metalhydrides, hydroxides, amides, alcoholates, carbonates or hydrogencarbonates, acetates or tertiary amines. More preferably, the base ischosen as being alkaline earth metal, alkali metal hydrides or alkalimetal alkides.

Compounds according to the present invention can be prepared accordingto the above described processes. It will nevertheless be understoodthat, on the basis of his general knowledge and of availablepublications, the skilled worker will be able to adapt these processesaccording to the specifics of each of the compounds which it is desiredto synthesise.

The present invention also relates to a fungicidal compositioncomprising an effective amount of an active material of general formula(I). Thus, according to the present invention, there is provided afungicidal composition comprising, as an active ingredient, an effectiveamount of a compound of general formula (I) as defined above and anagriculturally acceptable support, carrier or filler.

In the present specification, the term “support” denotes a natural orsynthetic, organic or inorganic material with which the active materialis combined to make it easier to apply, notably to the parts of theplant. This support is thus generally inert and should be agriculturallyacceptable. The support may be a solid or a liquid. Examples of suitablesupports include clays, natural or synthetic silicates, silica, resins,waxes, solid fertilisers, water, alcohols, in particular butanol,organic solvents, mineral and plant oils and derivatives thereof.Mixtures of such supports may also be used.

The composition may also comprise additional components. In particular,the composition may further comprise a surfactant. The surfactant can bean emulsifier, a dispersing agent or a wetting agent of ionic ornon-ionic type or a mixture of such surfactants. Mention may be made,for example, of polyacrylic acid salts, lignosulphonic acid salts,phenolsulphonic or naphthalenesulphonic acid salts, polycondensates ofethylene oxide with fatty alcohols or with fatty acids or with fattyamines, substituted phenols (in particular alkylphenols or arylphenols),salts of sulphosuccinic acid esters, taurine derivatives (in particularalkyl taurates), phosphoric esters of polyoxyethylated alcohols orphenols, fatty acid esters of polyols, and derivatives of the abovecompounds containing sulphate, sulphonate and phosphate functions. Thepresence of at least one surfactant is generally essential when theactive material and/or the inert support are water-insoluble and whenthe vector agent for the application is water. Preferably, surfactantcontent may be comprised between 5% and 40% by weight of thecomposition.

Optionally, additional components may also be included, e.g. protectivecolloids, adhesives, thickeners, thixotropic agents, penetration agents,stabilisers, sequestering agents. More generally, the active materialscan be combined with any solid or liquid additive, which complies withthe usual formulation techniques.

In general, the composition according to the invention may contain from0.05 to 99% (by weight) of active material, preferably 10 to 70% byweight.

Compositions according to the present invention can be used in variousforms such as aerosol dispenser, capsule suspension, cold foggingconcentrate, dustable powder, emulsifiable concentrate, emulsion oil inwater, emulsion water in oil, encapsulated granule, fine granule,flowable concentrate for seed treatment, gas (under pressure), gasgenerating product, granule, hot fogging concentrate, macrogranule,microgranule, oil dispersible powder, oil miscible flowable concentrate,oil miscible liquid, paste, plant rodlet, powder for dry seed treatment,seed coated with a pesticide, soluble concentrate, soluble powder,solution for seed treatment, suspension concentrate (flowableconcentrate), ultra low volume (ulv) liquid, ultra low volume (ulv)suspension, water dispersible granules or tablets, water dispersiblepowder for slurry treatment, water soluble granules or tablets, watersoluble powder for seed treatment and wettable powder.

These compositions include not only compositions which are ready to beapplied to the plant or seed to be treated by means of a suitabledevice, such as a spraying or dusting device, but also concentratedcommercial compositions which must be diluted before application to thecrop.

The compounds of the invention can also be mixed with one or moreinsecticides, fungicides, bactericides, attractant acaricides orpheromones or other compounds with biological activity. The mixturesthus obtained have a broadened spectrum of activity. The mixtures withother fungicides are particularly advantageous. Examples of suitablefungicide mixing partners may be selected in the following lists

1) a compound capable to inhibit the nucleic acid synthesis likebenalaxyl, benalaxyl-M, bupirimate, chiralaxyl, clozylacon,dimethirimol, ethirimol, furalaxyl, hymexazol, mefenoxam, metalaxyl,metalaxyl-M, ofurace, oxadixyl, oxolinic acid;

2) a compound capable to inhibit the mitosis and cell division likebenomyl, carbendazim, diethofencarb, ethaboxam, fuberidazole,pencycuron, thiabendazole thiophanate-methyl, zoxamide;

3) a compound capable to inhibit the respiration for example

as CI-respiration inhibitor like diflumetorim;

as CII-respiration inhibitor like boscalid, carboxin, fenfuram,flutolanil, furametpyr, furmecyclox, mepronil, oxycarboxine,penthiopyrad, thifluzamide;

as CIII-respiration inhibitor like amisulbrom, azoxystrobin, cyazofamid,dimoxystrobin, enestrobin, famoxadone, fenamidone, fluoxastrobin,kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,pyraclostrobin, trifloxystrobin;

4) a compound capable of to act as an uncoupler like dinocap, fluazinam,meptyldinocap;

5) a compound capable to inhibit ATP production like fentin acetate,fentin chloride, fentin hydroxide, silthiofam;

6) a compound capable to inhibit AA and protein biosynthesis likeandoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycinhydrochloride hydrate, mepanipyrim, pyrimethanil;

7) a compound capable to inhibit the signal transduction likefenpiclonil, fludioxonil, quinoxyfen;

8) a compound capable to inhibit lipid and membrane synthesis likebiphenyl, chlozolinate, edifenphos, iodocarb, iprobenfos, iprodione,isoprothiolane, procymidone, propamocarb, propamocarb hydrochloride,pyrazophos, tolclofos-methyl, vinclozolin;

9) a compound capable to inhibit ergosterol biosynthesis like aldimorph,azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole,difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorphacetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole,fenhexamid, fenpropidin, fenpropimorph, fluquinconazole, flurprimidol,flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole,imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole,myclobutanil, naftifine, nuarimol, oxpoconazole, paclobutrazol,pefurazoate, penconazole, prochloraz, propiconazole, prothioconazole,pyributicarb, pyrifenox, simeconazole, spiroxamine, tebuconazole,terbinafine, tetraconazole, triadimefon, triadimenol, tridemorph,triflumizole, triforine, triticonazole, uniconazole, viniconazole,voriconazole;

10) a compound capable to inhibit cell wall synthesis likebenthiavalicarb, bialaphos, dimethomorph, flumorph, iprovalicarb,polyoxins, polyoxorim, validamycin A;

11) a compound capable to inhibit melanine biosynthesis likecarpropamid, diclocymet, fenoxanil, phthalide, pyroquilon, tricyclazole;

12) a compound capable to induce a host defence likeacibenzolar-5-methyl, probenazole, tiadinil;

13) a compound capable to have a multisite action like Bordeaux mixture,captafol, captan, chlorothalonil, copper naphthenate, copper oxide,copper oxychloride, copper preparations such as copper hydroxide, coppersulphate, dichlofluanid, dithianon, dodine, dodine free base, ferbam,fluorofolpet, folpet, guazatine, guazatine acetate, iminoctadine,iminoctadine albesilate, iminoctadine triacetate, mancopper, mancozeb,maneb, metiram, metiram zinc, oxine-copper, propineb, sulphur andsulphur preparations including calcium polysulphide, thiram,tolylfluanid, zineb, ziram;

14) a compound selected in the following list:(2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylacetamide,(2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide,1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol,1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl1H-imidazole-1-carboxylate,2-(4-chlorophenyl)-N-{2-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]ethyl}-2-(prop-2-yn-1-yloxy)acetamide,2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine,2-butoxy-6-iodo-3-propyl-4H-chromen-4-one,2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)nicotinamide,2-phenylphenol and salts, 3,4,5-trichloropyridine-2,6-dicarbonitrile,3,4-dichloro-N-(2-cyanophenyl)isothiazole-5-carboxamide,3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine,5-chloro-6-(2,4,6-trifluorophenyl)-N-[(1R)-1,2,2-trimethylpropyl][1,2,4]triazolo[1,5-a]pyrimidin-7-amine,5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine,5-chloro-N-[(1R)-1,2-dimethylpropyl]-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidin-7-amine,8-hydroxyquinoline sulfate, benthiazole, bethoxazin, capsimycin,carvone, chinomethionat, cufraneb, cyflufenamid, cymoxanil, dazomet,debacarb, dichlorophen, diclomezine, dicloran, difenzoquat, difenzoquatmethylsulphate, diphenylamine, ferimzone, flumetover, fluopicolide,fluoroimide, flusulfamide, fosetyl-aluminium, fosetyl-calcium,fosetyl-sodium, hexachlorobenzene, irumamycin, methasulfocarb, methyl(2-chloro-5-{(1E)-N-[(6-methylpyridin-2-yl)methoxy]ethanimidoyl}benzyl)carbamate,methyl(2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}thio)methyl]phenyl}-3-methoxyacrylate,methyl1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate,methyl3-(4-chlorophenyl)-3-{[N-(isopropoxycarbonyl)valyl]amino}propanoate,methyl isothiocyanate, metrafenone, mildiomycin,N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide,N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide,N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloronicotinamide,N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloronicotinamide,N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodonicotinamide,N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N<sup>2</sup>-(methylsulfonyl)valinamide,N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide,N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamide,natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl,O-{1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl}1H-imidazole-1-carbothioate, octhilinone, oxamocarb, oxyfenthiin,pentachlorophenol and salts, phosphorous acid and its salts, piperalin,propamocarb fosetylate, propanosine-sodium, proquinazid, pyrrolnitrine,quintozene, tecloftalam, tecnazene, triazoxide, trichlamide andzarilamid.

The composition according to the invention comprising a mixture of acompound of formula (I) with a bactericide compound may also beparticularly advantageous. Examples of suitable bactericide mixingpartners may be selected in the following list: bronopol, dichlorophen,nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone,furancarboxylic acid, oxytetracycline, probenazole, streptomycin,tecloftalam, copper sulphate and other copper preparations.

The fungicidal compositions of the present invention can be used tocuratively or preventively control the phytopathogenic fungi of crops.Thus, according to a further aspect of the present invention, there isprovided a method for curatively or preventively controlling thephytopathogenic fungi of crops characterised in that a fungicidalcomposition as hereinbefore defined is applied to the seed, the plantand/or to the fruit of the plant or to the soil in which the plant isgrowing or in which it is desired to grow.

The composition as used against phytopathogenic fungi of crops comprisesan effective and non-phytotoxic amount of an active material of generalformula (I).

The expression “effective and non-phytotoxic amount” means an amount ofcomposition according to the invention which is sufficient to control ordestroy the fungi present or liable to appear on the crops, and whichdoes not entail any appreciable symptom of phytotoxicity for the saidcrops. Such an amount can vary within a wide range depending on thefungus to be controlled, the type of crop, the climatic conditions andthe compounds included in the fungicidal composition according to theinvention.

This amount can be determined by systematic field trials, which arewithin the capabilities of a person skilled in the art.

The method of treatment according to the present invention is useful totreat propagation material such as tubers or rhizomes, but also seeds,seedlings or seedlings pricking out and plants or plants pricking out.This method of treatment can also be useful to treat roots. The methodof treatment according to the present invention can also be useful totreat the overground parts of the plant such as trunks, stems or stalks,leaves, flowers and fruits of the concerned plant.

Among the plants that can be protected by the method according to thepresent invention, mention may be made of cotton; flax; vine; fruit orvegetable crops such as Rosaceae sp. (for instance pip fruit such asapples and pears, but also stone fruit such as apricots, almonds andpeaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp.,Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp.,Actimidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana treesand plantins), Rubiaceae sp., Theaceae sp., Sterculiceae sp., Rutaceaesp. (for instance lemons, oranges and grapefruit); Solanaceae sp. (forinstance tomatoes), Liliaceae sp., Asteraceae sp. (for instancelettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp.,Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp.(for instance strawberries); major crops such as Graminae sp. (forinstance maize, lawn or cereals such as wheat, rice, barley andtriticale), Asteraceae sp. (for instance sunflower), Cruciferae sp. (forinstance colza), Fabacae sp. (for instance peanuts), Papilionaceae sp.(for instance soybean), Solanaceae sp. (for instance potatoes),Chenopodiaceae sp. (for instance beetroots); horticultural and forestcrops; as well as genetically modified homologues of these crops.

Among the diseases of plants or crops that can be controlled by themethod according to the present invention, mention may be made of:

Powdery mildew diseases such as:

Blumeria diseases, caused for example by Blumeria graminis;

Podosphaera diseases, caused for example by Podosphaera leucotricha;

Sphaerotheca diseases, caused for example by Sphaerotheca fuliginea;

Uncinula diseases, caused for example by Uncinula necator;

Rust diseases such as:

Gymnosporangium diseases, caused for example by Gymnosporangium sabinae;

Hemileia diseases, caused for example by Hemileia vastatrix;

Phakopsora diseases, caused for example by Phakopsora pachyrhizi orPhakopsora meibomiae;

Puccinia diseases, caused for example by Puccinia recondita;

Uromyces diseases, caused for example by Uromyces appendiculatus;

Oomycete diseases such as:

Bremia diseases, caused for example by Bremia lactucae;

Peronospora diseases, caused for example by Peronospora pisi or P.brassicae;

Phytophthora diseases, caused for example by Phytophthora infestans;

Plasmopara diseases, caused for example by Plasmopara viticola;

Pseudoperonospora diseases, caused for example by Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Pythium diseases, caused for example by Pythium ultimum;

Leafspot, leaf blotch and leaf blight diseases such as:

Alternaria diseases, caused for example by Alternaria solani;

Cercospora diseases, caused for example by Cercospora beticola;

Cladiosporum diseases, caused for example by Cladiosporum cucumerinum;

Cochliobolus diseases, caused for example by Cochliobolus sativus;

Colletotrichum diseases, caused for example by Colletotrichumlindemuthanium;

Cycloconium diseases, caused for example by Cycloconium oleaginum;

Diaporthe diseases, caused for example by Diaporthe citri;

Elsinoe diseases, caused for example by Elsinoe fawcettii;

Gloeosporium diseases, caused for example by Gloeosporium laeticolor;

Glomerella diseases, caused for example by Glomerella cingulata;

Guignardia diseases, caused for example by Guignardia bidwehi;

Leptosphaeria diseases, caused for example by Leptosphaeria maculans;Leptosphaeria nodorum;

Magnaporthe diseases, caused for example by Magnaporthe grisea;

Mycosphaerella diseases, caused for example by Mycosphaerellagraminicola; Mycosphaerella arachidicola; Mycosphaerella fijiensis;

Phaeosphaeria diseases, caused for example by Phaeosphaeria nodorum;

Pyrenophora diseases, caused for example by Pyrenophora teres;

Ramularia diseases, caused for example by Ramularia collo-cygni;

Rhynchosporium diseases, caused for example by Rhynchosporium secalis;

Septoria diseases, caused for example by Septoria apii or Septorialycopercisi;

Typhula diseases, caused for example by Typhula incarnata;

Venturia diseases, caused for example by Venturia inaequalis;

Root and stem diseases such as:

Corticium diseases, caused for example by Corticium graminearum;

Fusarium diseases, caused for example by Fusarium oxysporum;

Gaeumannomyces diseases, caused for example by Gaeumannomyces graminis;

Rhizoctonia diseases, caused for example by Rhizoctonia solani;

Tapesia diseases, caused for example by Tapesia acuformis;

Thielaviopsis diseases, caused for example by Thielaviopsis basicola;

Ear and panicle diseases such as:

Alternaria diseases, caused for example by Alternaria spp.;

Aspergillus diseases, caused for example by Aspergillus flavus;

Cladosporium diseases, caused for example by Cladosporium spp.;

Claviceps diseases, caused for example by Claviceps purpurea;

Fusarium diseases, caused for example by Fusarium culmorum;

Gibberella diseases, caused for example by Gibberella zeae;

Monographella diseases, caused for example by Monographella nivalis;

Smut and bunt diseases such as:

Sphacelotheca diseases, caused for example by Sphacelotheca reiliana;

Tilletia diseases, caused for example by Tilletia caries;

Urocystis diseases, caused for example by Urocystis occulta;

Ustilago diseases, caused for example by Ustilago nuda;

Fruit rot and mould diseases such as:

Aspergillus diseases, caused for example by Aspergillus flavus;

Botrytis diseases, caused for example by Botrytis cinerea;

Penicillium diseases, caused for example by Penicillium expansum;

Sclerotinia diseases, caused for example by Sclerotinia sclerotiorum;

Verticilium diseases, caused for example by Verticilium alboatrum;

Seed and soilborne decay, mould, wilt, rot and damping-off diseases:

Fusarium diseases, caused for example by Fusarium culmorum;

Phytophthora diseases, caused for example by Phytophthora cactorum;

Pythium diseases, caused for example by Pythium ultimum;

Rhizoctonia diseases, caused for example by Rhizoctonia solani;

Sclerotium diseases, caused for example by Sclerotium rolfsii;

Microdochium diseases, caused for example by Microdochium nivale;

Canker, broom and dieback diseases such as:

Nectria diseases, caused for example by Nectria galligena;

Blight diseases such as:

Monilinia diseases, caused for example by Monilinia laxa;

Leaf blister or leaf curl diseases such as:

Taphrina diseases, caused for example by Taphrina deformans;

Decline diseases of wooden plants such as:

Esca diseases, caused for example by Phaemoniella clamydospora;

Diseases of flowers and Seeds such as:

Botrytis diseases, caused for example by Botrytis cinerea;

Diseases of tubers such as:

Rhizoctonia diseases, caused for example by Rhizoctonia solani.

The fungicide composition according to the present invention may also beused against fungal diseases liable to grow on or inside timber. Theterm “timber” means all types of species of wood, and all types ofworking of this wood intended for construction, for example solid wood,high-density wood, laminated wood, and plywood. The method for treatingtimber according to the invention mainly consists in contacting one ormore compounds of the present invention, or a composition according tothe invention; this includes for example direct application, spraying,dipping, injection or any other suitable means.

The dose of active material usually applied in the treatment accordingto the present invention is generally and advantageously between 10 and800 g/ha, preferably between 50 and 300 g/ha for applications in foliartreatment. The dose of active substance applied is generally andadvantageously between 2 and 200 g per 100 kg of seed, preferablybetween 3 and 150 g per 100 kg of seed in the case of seed treatment. Itis clearly understood that the doses indicated above are given asillustrative examples of the invention. A person skilled in the art willknow how to adapt the application doses according to the nature of thecrop to be treated.

The fungicidal composition according to the present invention may alsobe used in the treatment of genetically modified organisms with thecompounds according to the invention or the agrochemical compositionsaccording to the invention. Genetically modified plants are plants intowhose genome a heterologous gene encoding a protein of interest has beenstably integrated. The expression “heterologous gene encoding a proteinof interest” essentially means genes which give the transformed plantnew agronomic properties, or genes for improving the agronomic qualityof the transformed plant.

The compositions according to the present invention may also be used forthe preparation of composition useful to curatively or preventivelytreat human and animal fungal diseases such as, for example, mycoses,dermatoses, trichophyton diseases and candidiases or diseases caused byAspergillus spp., for example Aspergillus fumigatus.

The aspects of the present invention will now be illustrated withreference to the following tables of compounds and examples. Thefollowing Tables A to V illustrate in a non-limiting manner examples offungicidal compounds according to the present invention. In thefollowing Examples, M+1 (or M−1) means the molecular ion peak, plus orminus 1 a.m.u. (atomic mass units) respectively, as observed in massspectroscopy.

TABLE A

Compound n° X¹ X² X³ R¹ R² R³ R^(a) Y¹ Y² Y³ A (M + 1) A-1 Cl H Cl H H HH CHF₂ Me H Cis-cyclohexyl 403 A-2 Cl H Cl H H H H CHF₂ Me HTrans-cyclohexyl 403 A-3 Cl H Cl H H H H CHF₂ Me H cyclopropyl 361 A-4Cl H Cl H H H H Me Me F cyclopropyl 343

TABLE B

Compound n° X¹ X² X³ R¹ R² R³ R^(a) Y¹ Y² Y³ Y⁴ A (M + 1) B-1 Cl H Cl HH H H Cl H H H Trans-cyclopropyl 340

TABLE C

Compound n° X¹ X² X³ R¹ R² R³ R^(a) Y¹ Y² Y³ A (M + 1) C-1 Cl H Cl H H HH I H H Trans-cyclopropyl 439

EXAMPLES OF PROCESS FOR THE PREPARATION OF THE COMPOUND OF GENERALFORMULA (I) Example 1 Preparation ofN-{2-[3,5-dichloro-2-pyridinyl]trans-cyclohexyl}1-methyl-3-(difluoromethyl)-1H-pyrazole-4-carboxamide(Compound A-1) andN-{2-[3,5-dichloro-2-pyridinyl]cis-cyclohexyl}1-methyl-3-(difluoromethyl)-1H-pyrazole-4-carboxamide(Compound A-2) Preparation of 2-[3,5-dichloro-2-pyridinyl]cyclohexanone

5.00 g (0.030 mol) of 3,5-dichloro-2-fluoropyridine and 5.01 g of1-(1-cyclohexen-1-yl)pyrrolidine (0.033 mol) are stirred neat togetherat room temperature for 1 h and are left at room temperature overnight.The reaction mixture is quenched with 40 ml of sulfuric acid 2M. Wateris added to the reaction mixture (100 ml) which is extracted thrice withethyl acetate (50 ml). The combined organic phases are washed with water(150 ml) and brine (100 ml). After separation, the organic phase isdried over magnesium sulfate filtered, concentrated to dryness andpurified on silica gel to yield to 0.22 g of2-[3,5-dichloro-2-pyridinyl]cyclohexanone (2%).

Mass spectrum: [M+1]=244.

Preparation of 2-[3,5-dichloro-2-pyridinyl]cyclohexanamine hydrochloride

0.22 g (0.86 mmol) of 2-[3,5-dichloro-2-pyridinyl]cyclohexanone, 0.2 gof molecular sieves 3 Å, 0.53 g (6.85 mmol) of ammonium acetate arerefluxed in 5 mL of methanol for 3 hours. Back at room temperature, 93mg (0.018 mol) of sodium cyanoborohydride are added, the reactionmixture is refluxed for one hour and left overnight at room temperature.The medium is filtered, concentrated to dryness and 10 ml of aqueoussodium hydroxide 1M is added. The aqueous phase is extracted thrice with10 ml of dichloromethane. The combined organic phases are washed twicewith 10 ml of water, dried over magnesium sulfate, filtered andconcentrated. 3 ml of a solution of hydrogen chloride in diethyl ether(1M) are added to the crude material. The precipitate is filtered andwashed with diethyl ether to yield to 0.15 g of2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]cyclohexanaminehydrochloride (56%).

Mass spectrum: [M+1−36]=245.

Preparation ofN-{2-[3,5-dichloro-2-pyridinyl]trans-cyclohexyl}1-methyl-3-(difluoromethyl)-1H-pyrazole-4-carboxamide(Compound A-1) andN-{2-[3,5-dichloro-2-pyridinyl]cis-cyclohexyl}1-methyl-3-(difluoromethyl)-1H-pyrazole-4-carboxamide(Compound A-2)

0.031 g of oxalyl chloride (0.0025 mmol) is diluted in a 2 ml ofdichloromethane. A drop of dimethylformamide is added to the reactionmixture. After 30 min of stirring at room temperature, 0.70 g of2-[3,5-dichloro-2-pyridinyl]cyclohexanamine hydrochloride (0.00022 mol),0.07 ml of triethylamine are added to the reaction mixture which isstirred at room temperature overnight. Dichloromethane is added (5 ml)to the reaction mixture, which is washed twice with water (5 ml). Afterseparation, the organic phase is dried over magnesium sulfate, filtered,concentrated to dryness and purified on silica to yield to:

42 mg ofN-{2-[3,5-dichloro-2-pyridinyl]cis-cyclohexyl}1-methyl-3-(difluoromethyl)-1H-pyrazole-4-carboxamide(44%) (mass spectrum: [M+1]=417); and

20 mg ofN-{2-[3,5-dichloro-2-pyridinyl]trans-cyclohexyl}1-methyl-3-(difluoromethyl)-1H-pyrazole-4-carboxamide(21%) (mass spectrum: [M+1]=417).

Example 2 Preparation ofN-[2-(3,5-dichloropyridin-2-yl)cyclopropyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide(Compound A-3) Preparation of 3,5-dichloro-2-vinylpyridine

20.06 g of 3,5-dichloro-2-fluoropyridine (0.110 mol), 30.46 ml oftributyl-vinyl-stannane (0.103 mol), 6.00 g (0.00518 mol) of Pd(PPh₃)₄are refluxed in 400 ml of toluene for five hours. The reaction mixtureis washed thrice with a saturated aqueous solution of potassium fluoride200 ml), once with water (300 ml), once with brine (300 ml). Thecombined aqueous phases are extracted with 100 ml of toluene. Afterseparation, the combined organic phases are dried over magnesiumsulfate, filtered, concentrated to dryness and purified on silica toyield to 15.05 g of 3,5-dichloro-2-vinylpyridine (62%) with 75% purity.

Mass spectrum: [M+1]=174.

Preparation of ethyl 2-(3,5-dichloropyridin-2-yl)cyclopropanecarboxylate

A mixture of 0.485 g of 3,5-dichloro-2-vinylpyridine (0.0014 mol) and0.15 ml of ethyl diazoacetate (0.00127 mol) are added dropwise to 5 mlof refluxing xylene. The reaction mixture is refluxed for thirty minutesand left at room temperature overnight. After concentration to drynessand purification on silica, 250 mg of essentially pure ethyl2-(3,5-dichloropyridin-2-yl)cyclopropanecarboxylate (75%) are obtained.

Mass spectrum: [M+1]=260.

Preparation of 2-(3,5-dichloropyridin-2-yl)cyclopropanecarboxylic acid

1.65 g of ethyl 2-(3,5-dichloropyridin-2-yl)cyclopropanecarboxylate(0.00634 mol) are dissolved in 20 ml of ethanol, 9.5 ml of sodiumhydroxide 1M are added to the reaction mixture which is refluxed for 4hours and left at room temperature overnight. After concentration invacuo, 30 ml of water are added to the reaction mixture which isextracted twice with ethyl acetate (20 ml). The aqueous phase isacidified with HCl 1M. The precipate which forms is filtered, air-driedto yield to 1.35 g of 2-(3,5-dichloropyridin-2-yl)cyclopropanecarboxylicacid (87%).

Mass spectrum: [M+1]=232.

Preparation of tert-butyl[2-(3,5-dichloropyridin-2-yl)cyclopropyl]carbamate

1.76 g of 2-(3,5-dichloropyridin-2-yl)cyclopropanecarboxylic acid(0.00758 mol), 1.17 ml of triethylamine (0.00834 mol), 2.50 g (0.00901mol) of diphenyl-phosphoryl azide are refluxed for 4 hours in 25 ml oftert-butanol.

At room temperature, the reaction mixture is quenched with 100 ml ofwater and 10 ml of a solution of saturated sodium bicarbonate. Afterseparation, the aqueous phase is extracted twice with 50 ml of ethylacetate. The combined organic phases are dried over magnesium sulfate,filtered, concentrated to dryness and purified on silica to yield to1.23 g of tert-butyl [2-(3,5-dichloropyridin-2-yl)cyclopropyl]carbamate(48%).

Mass spectrum: [M+1]=303.

Preparation of tert-butyl[2-(3,5-dichloropyridin-2-yl)cyclopropyl]{[3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]carbonyl}carbamate

Under argon, 0.50 g of tert-butyl[2-(3,5-dichloropyridin-2-yl)cyclopropyl]carbamate (0.00148 mol), aredissolved in 10 ml of tetrahydrofuran at −70° C. n-butyllithium (0.00226mol) in solution in hexanes is added. After 5 minutes of stirring at−70° C., 0.46 g of 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonylchloride (0.00166 mol) in solution in 50 ml of tetrahydrofuran are addeddropwise. The reaction mixture is stirred at −70° C. for two hours andthen allowed to room temperature overnight.

The reaction mixture is quenched with 50 ml of a solution of saturatedammonium chloride. After separation, the aqueous phase is extractedtwice with 20 ml of ethyl acetate. The combined organic phases are driedover magnesium sulfate, filtered, concentrated to dryness and purifiedon silica to yield to 205 mg of tert-butyl[2-(3,5-dichloropyridin-2-yl)cyclopropyl]{[3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]carbonyl}carbamate(26%).

Mass spectrum: [M+1]=461.

Preparation ofN-[2-(3,5-dichloropyridin-2-yl)cyclopropyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide(Compound A-3)

0.200 g of tert-butyl[2-(3,5-dichloropyridin-2-yl)cyclopropyl]{[3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]carbonyl}carbamate(0.00039 mol) are dissolved in 5 ml of dichloromethane. 0.50 ml oftrifluoroacetic acid are added to the reaction mixture which is leftstirring at room temperature overnight. The reaction mixture is quenchedwith 15 ml of an aqueous solution of saturated sodium bicarbonate. Afterseparation, the aqueous phase is extracted with dichloromethane (10 ml).The combined organic phases are dried over magnesium sulfate, filtered,concentrated to dryness and purified on silica to yield to 120 mg ofN-[2-(3,5-dichloropyridin-2-yl)cyclopropyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide(76%).

Mass spectrum: [M+1]=361.

Examples of Biological Activity of the Compound of General Formula (I)Example A In Vivo Test on Alternaria brassicae (Leaf Spot of Crucifers)

The active ingredients tested are prepared by homogenization in amixture of DMSO (dimethylsulfoxide)/acetone/tween/water. This suspensionis then diluted with water to obtain the desired active materialconcentration.

Radish plants (Pernot variety) in starter cups, sown on a 50/50 peatsoil-pozzolana substrate and grown at 18-20° C., are treated at thecotyledon stage by spraying with the aqueous suspension described above.

Plants, used as controls, are treated with an aqueous solution notcontaining the active material.

After 24 hours, the plants are contaminated by spraying them with anaqueous suspension of Alternaria brassicae spores (40,000 spores percm³). The spores are collected from a 12-13-day-old culture.

The contaminated radish plants are incubated for 6-7 days at about 18°C., under a humid atmosphere.

Grading is carried out 6 to 7 days after the contamination, incomparison with the control plants.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm with the following compounds: A-1 and A-3.

Example B In Vivo Test on Pyrenophora teres (Barley Net Blotch)

The active ingredients tested are prepared by homogenization in amixture of DMSO (dimethylsulfoxide)/acetone/tween/water. This suspensionis then diluted with water to obtain the desired active materialconcentration.

Barley plants (Express or Plaisant variety) in starter cups, sown on a50/50 peat soil-pozzolana substrate and grown at 12° C., are treated atthe 1-leaf stage (10 cm tall) by spraying with the aqueous suspensiondescribed above. Plants, used as controls, are treated with an aqueoussolution not containing the active material.

After 24 hours, the plants are contaminated by spraying them with anaqueous suspension of Pyrenophora teres spores (12,000 spores per ml).The spores are collected from a 12-day-old culture. The contaminatedbarley plants are incubated for 24 hours at about 20° C. and at 100%relative humidity, and then for 12 days at 80% relative humidity.

Grading is carried out 12 days after the contamination, in comparisonwith the control plants.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm with the following compounds: A-1, A-3,A-4, B-1 and C-1.

Example C In Vivo Test on Botrylis cinerea (Gherkin Grey Mould)

The active ingredients tested are prepared by homogenization in amixture of DMSO (dimethylsulfoxide)/acetone/tween/water. This suspensionis then diluted with water to obtain the desired active materialconcentration.

Gherkin plants (Petit Vert de Paris variety) in starter cups, sown on a50/50 peat soil-pozzolana substrate and grown at 18-20° C., are treatedat the cotyledon Z11 stage by spraying with the aqueous suspensiondescribed above. Plants, used as controls, are treated with an aqueoussolution not containing the active material.

After 24 hours, the plants are contaminated by depositing drops of anaqueous suspension of Botrytis cinerea spores (150,000 spores per ml) onupper surface of the leaves. The spores are collected from a 15-day-oldculture and are suspended in a nutrient solution composed of:

-   -   20 g/L of gelatin    -   50 g/L of cane sugar    -   2 g/L of NH4NO3    -   1 g/L of KH2PO4

The contaminated gherkin plants are settled for 5/7 days in a climaticroom at 15-11° C. (day/night) and at 80% relative humidity.

Grading is carried out 5/7 days after the contamination, in comparisonwith the control plants.

Under these conditions, good (at least 70%) or total protection isobserved at a dose of 500 or 125 ppm with the following compounds: A-3,B-1 and C-1.

Example D In Vivo Test on Sphaerotheca fuliginea (Powdery Mildew)

The active ingredients tested are prepared by homogenization in amixture of DMSO (dimethylsulfoxide)/acetone/tween/water. This suspensionis then diluted with water to obtain the desired active materialconcentration.

Gherkin plants (Vert petit de Paris variety) in starter cups, sown on a50/50 peat soil-pozzolana substrate and grown at 20° C./23° C., aretreated at cotyledons stage by spraying with the aqueous suspensiondescribed above. Plants, used as controls, are treated with an aqueoussolution not containing the active material.

After 24 hours, the plants are contaminated by spraying them with anaqueous suspension of Sphaerotheca fuliginea spores (100 000 spores perml). The spores are collected from a contaminated plants. Thecontaminated gerkhin plants are incubated at about 20° C./25° C. and at60/70% relative humidity.

Grading (% of efficacy) is carried out 13 days after the contamination,in comparison with the control plants.

Under these conditions, good (at least 70%) is observed at a dose of 600g/ha with the following compound: A-2.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 125 ppm with the following compounds: A-3 and C-1.

1. A compound of formula (I)

in which: n is 1, 2, or 3; each X is independently selected from thegroup consisting of a hydrogen atom, a halogen atom, a nitro group, acyano group, a hydroxy group, an amino group, a sulfanyl group, apentafluoro-λ⁶-sulfanyl group, a formyl group, a formyloxy group, aformylamino group, a carboxy group, a carbamoyl group, aN-hydroxycarbamoyl group, a carbamate group, a(hydroxyimino)-C₁-C₆-alkyl group, a C₁-C₈-alkyl, a C₂-C₈-alkenyl, aC₂-C₈-alkynyl, a C₁-C₈-alkylamino, a di-C₁-C₈-alkylamino, aC₁-C₈-alkoxy, a C₁-C₈-halogenoalkoxy having 1 to 5 halogen atoms, aC₁-C₈-alkylsulfanyl, a C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogenatoms, a C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1 to 5halogen atoms, a C₃-C₈-alkynyloxy, a C₃-C₈-halogenoalkynyloxy having 1to 5 halogen atoms, a C₃-C₈-cycloalkyl, a C₃-C₈-halogenocycloalkylhaving 1 to 5 halogen atoms, a C₁-C₈-alkylcarbonyl, aC₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms, aC₁-C₈alkylcarbamoyl, a di-C₁-C₈-alkylcarbamoyl, a(N—C₁-C₈-alkyl)oxycarbamoyl, a C₁-C₈-alkoxycarbamoyl, a(N—C₁-C₈-alkyl)-C₁-C₃-alkoxycarbamoyl, a C₁-C₈-alkoxycarbonyl, aC₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, aC₁-C₈-alkylcarbonyloxy, a C₁-C₈-halogenoalkylcarbonyloxy having 1 to 5halogen atoms, a C₁-C₈-alkylcarbonylamino, aC₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, aC₁-C₈-alkylaminocarbonyloxy, a di-C₁-C₈-alkylaminocarbonyloxy, aC₁-C₈-alkyloxycarbonyloxy, a C₁-C₈-alkylsulfenyl, aC₁-C₈-halogenoalkylsulfenyl having 1 to 5 halogen atoms, aC₁-C₈-alkylsulfinyl, a C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogenatoms, a C₁-C₈-alkylsulfonyl, a C₁-C₈-halogenoalkylsulfonyl having 1 to5 halogen atoms, a (C₁-C₆-alkoxyimino)-C₁-C₆-alkyl, a(C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl, a(C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl, a (benzyloxyimino)-C₁-C₆-alkyl, abenzyloxy, a benzylsulfanyl, a benzylamino, a phenoxy, a phenylsulfanyl,and a phenylamino; R^(a) is selected from the group consisting of ahydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxygroup, a sulfanyl group, a pentafluoro-λ⁶-sulfanyl group, a formylgroup, a formyloxy group, a formylamino group, a carboxy group, acarbamoyl group, a N-hydroxycarbamoyl group, a carbamate group, a(hydroxyimino)-C₁-C₆-alkyl group, a C₁-C₈-alkyl, a C₂-C₈-alkenyl, aC₂-C₈-alkynyl, a C₁-C₈-alkylamino, a di-C₁-C₈-alkylamino, aC₁-C₈-alkoxy, a C₁-C₈-halogenoalkoxy having 1 to 5 halogen atoms, aC₁-C₈-alkylsulfanyl, a C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogenatoms, a C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1 to 5halogen atoms, a C₃-C₈-alkynyloxy, a C₃-C₈-halogenoalkynyloxy having 1to 5 halogen atoms, a C₃-C₈-cycloalkyl, a C₃-C₈-halogenocycloalkylhaving 1 to 5 halogen atoms, a C₁-C₈-alkylcarbonyl, aC₁-C₈-halogenoalkylcarbonyl having 1 to 5 halogen atoms, aC₁-C₈-alkylcarbamoyl, a di-C₁-C₈-alkylcarbamoyl, aN—C₁-C₈-alkyloxycarbamoyl, a C₁-C₈-alkoxycarbamoyl, aN—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl, a C₁-C₈-alkoxycarbonyl, aC₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, aC₁-C₈-alkylcarbonyloxy, a C₁-C₈-halogenoalkylcarbonyloxy having 1 to 5halogen atoms, a C₁-C₈-alkylcarbonylamino, aC₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, aC₁-C₈-alkylaminocarbonyloxy, a di-C₁-C₈-alkylaminocarbonyloxy, aC₁-C₈-alkyloxycarbonyloxy, a C₁-C₈-alkylsulfenyl, aC₁-C₈-halogenoalkylsulfenyl having 1 to 5 halogen atoms, aC₁-C₈-alkylsulfinyl, a C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogenatoms, a C₁-C₈-alkylsulfonyl, a C₁-C₈-halogenoalkylsulfonyl having 1 to5 halogen atoms, a (C₁-C₆-alkoxyimino)-C₁-C₆-alkyl, a(C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl, a(C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl, a (benzyloxyimino)-C₁-C₆-alkyl, abenzyloxy, a benzylsulfanyl, a benzylamino, a phenoxy, a phenylsulfanyl,and a phenylamino; A is a 3-, 4-, 5-, 6- or 7-membered non-aromaticcarbocycle; R¹ and R² are independently selected from the groupconsisting of a hydrogen atom, a halogen atom, a cyano group, a hydroxygroup, an amino group, a sulfanyl group, a formyl group, a formyloxygroup, a formylamino group, a carboxy group, a carbamoyl group, aN-hydroxycarbamoyl group, a carbamate group, a(hydroxyimino)-C₁-C₆-alkyl group, a C₁-C₆-alkyl, a C₂-C₆-alkenyl, aC₂-C₆-alkynyl, a C₁-C₆-alkylamino, a di-C₁-C₆-alkylamino, aC₁-C₆-alkoxy, a C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms, aC₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₆-alkylsulfanyl,a C₁-C₆-halogenoalkylsulfanyl having 1 to 5 halogen atoms, aC₂-C₆-alkenyloxy, a C₂-C₆-halogenoalkenyloxy having 1 to 5 halogenatoms, a C₃-C₆-alkynyloxy, a C₃-C₆-halogenoalkynyloxy having 1 to 5halogen atoms, a C₃-C₆-cycloalkyl, a C₃-C₆-halogenocycloalkyl having 1to 5 halogen atoms, a C₁-C₆-alkylcarbonyl, a C₁-C₆-halogenoalkylcarbonylhaving 1 to 5 halogen atoms, a C₁-C₆-alkylcarbamoyl, adi-C₁-C₆-alkylcarbamoyl, a N—C₁-C₆-alkyloxycarbamoyl, aC₁-C₆-alkoxycarbamoyl, a N—C₁-C₆-alkyl-C₁-C₆-alkoxycarbamoyl, aC₁-C₆-alkoxycarbonyl, a C₁-C₆-halogenoalkoxycarbonyl having 1 to 5halogen atoms, a C₁-C₆-alkylcarbonyloxy, aC₁-C₆-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, aC₁-C₆-alkylcarbonylamino, a C₁-C₆-halogenoalkylcarbonylamino having 1 to5 halogen atoms, a C₁-C₆-alkylaminocarbonyloxy, adi-C₁-C₆-alkylaminocarbonyloxy, a C₁-C₆-alkyloxycarbonyloxy, aC₁-C₆-alkylsulfenyl, a C₁-C₆-halogenoalkylsulfenyl having 1 to 5 halogenatoms, a C₁-C₆-alkylsulfinyl, a C₁-C₆-halogenoalkylsulfinyl having 1 to5 halogen atoms, a C₁-C₆-alkylsulfonyl, a C₁-C₆-halogenoalkylsulfonylhaving 1 to 5 halogen atoms, a benzyl, a benzyloxy, a benzylsulfanyl, abenzylsulfinyl, a benzylsulfonyl, a benzylamino, a phenoxy, aphenylsulfanyl, a phenylsulfinyl, a phenylsulfonyl, a phenylamino, aphenylcarbonylamino, a 2,6 dichlorophenyl-carbonylamino group, and aphenyl group, R³ is selected from the group consisting of a hydrogenatom, a cyano group, a formyl group, a hydroxy group, a C₁-C₆-alkyl, aC₁-C₆-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₆-alkoxy, aC₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, aC₃-C₆-halogenocycloalkyl having 1 to 5 halogen atoms, a C₂-C₆-alkenyl, aC₂-C₆-alkynyl, a C₁-C₆-alkoxy-C₁-C₆-alkyl, a C₁-C₆-cyanoalkyl, aC₁-C₆-aminoalkyl, a C₁-C₆-alkylamino-C₁-C₆-alkyl, adi-C₁-C₆-alkylamino-C₁-C₆-alkyl, a C₁-C₆-alkylcarbonyl, aC₁-C₆-halogenalkylcarbonyl having 1 to 5 halogen atoms, aC₁-C₆-alkyloxycarbonyl, a C₃-C₇-cycloalkyl, a C₃-C₇-halogenocycloalkylhaving 1 to 5 halogen atoms, a C₃-C₇-cycloalkyl-C₁-C₆-alkyl, aC₁-C₆-benzyloxycarbonyl, a C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl, aC₁-C₆-alkylsulfonyl, and a C₁-C₆-halogenoalkylsulfonyl having 1 to 5halogen atoms; R³⁷ is selected from the group consisting of a hydrogenatom, a halogen atom, a cyano group, a nitro group, a C₁-C₄-alkyl, aC₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₃-C₆-cycloalkyl, aC₁-C₄-alkoxy, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, aC₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms,an aminocarbonyl and an aminocarbonyl-C₁-C₄-alkyl; R³⁸ is selected fromthe group consisting of a hydrogen atom, a halogen atom, a cyano group,a C₁-C₄-alkyl, a C₁-C₄-alkoxy, a C₁-C₄-halogenoalkoxy having 1 to 5halogen atoms and a C₁-C₄-alkylthio; and R³⁹ is selected from the groupconsisting of a hydrogen atom, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkylhaving 1 to 5 halogen atoms, a hydroxy-C₁-C₄-alkyl, a C₂-C₆-alkenyl, aC₃-C₆-cycloalkyl, a C₁-C₄-alkylthio-C₁-C₄-alkyl, aC₁-C₄-halogenoalkylthio-C₁-C₄-alkyl having 1 to 5 halogen atoms, aC₁-C₄-alkoxy-C₁-C₄-alkyl, a C₁-C₄-halogenoalkoxy-C₁-C₄-alkyl having 1 to5 halogen atoms or a phenyl optionally substituted by a halogen atom, aC₁-C₄-alkyl, a C₁-C₄-alkoxyalkyl and a nitro group; provided that R³⁷and R³⁸ are not both hydrogen atoms; as well as any salt, N-oxide, oroptically active isomer thereof.
 2. The compound of claim 1 whereinR^(a) is selected from the group consisting of a hydrogen atom and ahalogen atom.
 3. The compound of claim 1 wherein n is 1 or
 2. 4. Thecompound of claim 1 wherein X is selected from the group consisting of ahalogen atom and a C₁-C₈-alkyl.
 5. The compound of claim 1 wherein the2-pyridyl moiety is substituted by X in the 3- and/or in the 5-position.6. The compound of claim 1 wherein A is selected from the groupconsisting of cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl. 7.The compound of claim 1 wherein R¹ and R² are independently selectedfrom the group consisting of a hydrogen atom, a halogen atom, a cyanogroup, a hydroxy group, a C₁-C₆-alkyl, a C₁-C₆-halogenoalkyl having 1 to5 halogen atoms, a C₂-C₆-alkenyl, a C₁-C₆-alkoxy, a C₁-C₆-alkylsulfanyl,a C₁-C₆-alkylsulfenyl, a C₁-C₆-alkylsulfinyl, a C₁-C₆-alkoxycarbonyl, aC₁-C₆-alkylcarbonylamino, a C₁-C₆-alkoxycarbonyloxy, aC₁-C₆-alkoxycarbonylamino, and a phenyl group.
 8. The compound of claim1 wherein R³ is selected from the group consisting of a hydrogen atom,and a C₃-C₇-cycloalkyl.
 9. A fungicide composition comprising aneffective amount of the compound of claim 1 and an agriculturallyacceptable support.
 10. A method for combating the phytopathogenic fungiof crops comprising applying an effective and non-phytotoxic amount ofthe composition of claim 9 to the plant seeds or to the plant leavesand/or to the fruits of the plants or to the soil in which the plantsare growing or in which it is desired to grow them.
 11. The compound ofclaim 1 wherein R³⁷ is selected from the group consisting of C₁-C₄-alkyland C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.
 12. The compound ofclaim 1 wherein R³⁸ is selected from the group consisting of a hydrogenatom and a halogen atom.
 13. The compound of claim 1 wherein R³⁹ is aC₁-C₄-alkyl.
 14. The compound of claim 1 wherein: R³⁷ is selected fromthe group consisting of C₁-C₄-alkyl and C₁-C₄-halogenoalkyl having 1 to5 halogen atoms; R³⁸ is selected from the group consisting of a hydrogenatom and a halogen atom; and R³⁹ is a C₁-C₄-alkyl.
 15. The compound ofclaim 1 wherein: n is 2; each X is a chlorine atom; R¹, R², R³, andR^(a) are hydrogen atoms; R³⁷ is CHF₂ or methyl; R³⁸ is hydrogen orfluorine; R³⁹ is methyl; and A is selected from the group consisting ofcis-cyclohexyl, trans-cyclohexyl, and cyclopropyl.
 16. A fungicidecomposition comprising an effective amount of the compound of claim 15and an agriculturally acceptable support.
 17. A method for combating thephytopathogenic fungi of crops comprising applying an effective andnon-phytotoxic amount of the composition of claim 16 to the plant seedsor to the plant leaves and/or to the fruits of the plants or to the soilin which the plants are growing or in which it is desired to grow them.18. The compound of claim 15 wherein R³⁷ is CHF₂, R³⁸ is hydrogen, and Ais cyclopropyl.
 19. A fungicide composition comprising an effectiveamount of the compound of claim 18 and an agriculturally acceptablesupport.
 20. A method for combating the phytopathogenic fungi of cropscomprising applying an effective and non-phytotoxic amount of thecomposition of claim 19 to the plant seeds or to the plant leaves and/orto the fruits of the plants or to the soil in which the plants aregrowing or in which it is desired to grow them.